JPS60228567A - Isothiazolic azo dye - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention The present invention is based on the general formula (wherein R is a hydrogen atom, a 01-C4-alkyl group, or an optionally substituted phenyl group, and R1 is an allyl group, an optionally substituted alkyl group) , a cycloalkyl group or an aryl group, R2 is an acyl group, R1 and R2 may also be combined with a nitrogen atom to form a saturated 5- or 6-membered ring or a diacylimide group, and K is the remainder of the coupling component. (meaning a group).

Individual examples of H include hydrogen atoms and the following groups. Butyl, furovyl, ethyl, phenyl, chlorphenyl, methylphenyl, methoxyphenyl, nitrophenyl and preferably methyl.

Examples of R1 are 01-C8-alkyl, which may be further interrupted by an oxygen atom, and C0-C8-alkoxy, phenoxy, phenyl or 01-C8-
optionally substituted by alkanoyloxy/groups),
There are cyclopentyl group, cyclohexyl group, methylcyclohexyl group, etc.

Individual examples of R1 include the following groups in addition to those mentioned above. C
H3, C2H5, C3H7, C4H9, c, HI3, C
8H1? , C2H,0CH2CH2, CH30CH2C
O1CH3, C4H0OCH2CH2CH2, CH3C
ONHCH2CH2, C2H50COCH2, CH30
COCHCH3,C,H,0CH2CH2,C6H,0
CH2CH20CH2CH2CH2, C6HiCH2-
Groups that can exist as isomers include compounds of the type indicated by the abbreviations n-11- and t-.

An example of R2 is: 01-C1°-alkanoyl group (which may be further substituted with an alkoxy group or mafenoxy group), a cyclohexanoyl group, a benzyl group optionally substituted with a chlorine atom, a methyl group or a methoxy group groups, C1-C8-alkoxycarbonyl groups, aminocarbonyl groups, optionally N-mono- or N,N-disubstituted aminocarbonyl groups or -, aryl- or aminosulfonyl groups.

Individual R20 examples are as follows. CHO1CH3Co
.

CH3 ■ CH30CH2CO1CH3-C-Co, C5H7CO
1C7H,,Co.

CH3 C,H,, Co, C6H60CH2Co, C6H,
CH2Co, C6H3CH=CH-Co, l CH30CO1C2H,0CO1C4H,OCO,C8
H,OCO.

CH30CH2CH20CO+CH3IIJT(CO+
C2H3NHCO1C3H9NHCO1C4H,NHC
Ol(CH3)2NCO, CH35o2, C, H, So
Examples of groups formed by □ or R1 and R2 together with a nitrogen atom are as follows.

The coupling component KH is in particular aniline, naphthalene or heterocyclic. In particular, KH is preferably expressed by the following formula.

In this formula, R3 is a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, R4 is a hydrogen atom or the same as R5,
R5 is an optionally substituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl group,
R6 and R7 are hydrogen atoms, alkyl groups, alkoxy groups,
phenoxy group, halogen atom, alkylsulfonylamino group, dialkylaminosulfonylamino group, or acylamino group; R8 is a cyan group, carbamoyl group, nitro group, or carbalkoxy group; socite R0 is an optionally substituted phenyl group, alkyl group, or alkyl group; It is an alkyl group.

In addition to those mentioned above, individual examples of R3 include the following groups. Methyl, ethyl, propyl, butyl, and PerR5 are as follows. 01-C6-alkyl group (this is a chlorine atom, bromine atom, hydroxyl group, C8-C8-alkoxy group, phenoxy group, cyan group, carboxy group, cI-
C8-alkanoyloxy group, 01-C8-alkoxy-01-c4-alkoxy group, benzoyloxy group, o
-1m-1p-methylbenzoyloxy group, o-1m-
1p-chlorobenzoyloxy group, CI-c8-alkoxyalkanoyloxy group, phenoxyalkanoyloxy group, 01-c8-alkoxycarbonyloxy group,
01-c8-alkoxyalkoxycarbonyloxy group, benzyloxycarbonyloxy group, phenethyloxycarbonyloxy group, phenoxyethoxycarbonyloxy group, C,% C8-alkylaminocarbonyloxy group, cyclohexylaminocarbonyloxy group, phenylaminocarbonyloxy group , C, ~Cs phenoxycarbonyl group, c, ~c8-alkoxyalkoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, phenoxy-C, ~C4-alkoxy group or phenethyloxycarbonyl group) , phenyl group, benzyl group, phenylethyl group or cyclohexyl group.

Specific examples of R5 are the following groups: Methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methalyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,6-cyhydroxyglobil , 2-
Hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-6-fethuxiprovir, 2-hydroxy-3
-methoxyglobil, 2-hydroxy-3-butoxypropyl, 6-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-
Methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-Ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-methylaminecarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2- Butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-
Ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-proxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-β-phenylethoxycarbonylethyl, 2
-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl or 2-benzoylethyl.

Examples of R6 and R7 are a hydrogen atom, a methyl group, an ethyl group,
Propyl group, bromine atom, chlorine atom, methoxy group, ethoxy group, phenoxy group, benzyloxy group, 01-C6-
Alkanoylami 7 groups, benzylamino group, CI-C4
-alkylsulfonylamine group or -dialkylsulfonylamino group.

Examples of R8 include the following groups in addition to those mentioned above. Aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n
- and i-propoxycarbonyl, n-, i- and secondary butoxycarbonyl, methoxyethoxycarbonyl,
Ethoxyethoxycarbonyl, n- and 7J i-proboxyethoxycarbonyl or n-1i- and secondary butoxyethoxycarbonyl.

Examples of R9 are 01-Cl0-alkyl group, 01-C,.

-Alkoxy group, phenoxy group, benzyloxy group, phenyl group, chlorine atom, bromine atom, nitro group, C8-C4
-alkoxycarbonyl group, CI-C4-mono- or dialkylamino group, C1-C.

- a phenyl group substituted by one or more alkoxyethoxy groups, 01-C4-alkyl- or phenylmercapto groups, C1-C6-alkanoylamino groups, such as acetylamino, propionylamino, butyrylamino or valerylamino groups. , C1-C4-alkyl group, c', -C2-alkoxycarbonylmethyl group, cyanomethyl group or benzyl group.

The compounds of the formula I have a yellow to blue shade and are particularly suitable for dyeing polyesters, polyamides, cellulose esters and blended fabrics from polyester and cellulose fibres. Dyeings with good fastness properties are usually obtained on polyester.

To prepare compounds of formula I, a diazonium compound of an amine of the formula is reacted with a coupling component of the formula KH in a conventional manner.

Preparation details are given in the examples, in which parts and percentages are by weight unless otherwise indicated.

Of particular interest are compounds of the formula: In this formula, B1 is 00 to Cδ
-Alkyl group, B2 is an acyl group Kl is a residue of an aniline-based or thiazole-based camping component.

A particularly preferred coupling component 'H is represented by the following formula.

H3 Example 1 11.9 parts of 5-amino-4-cyano-6-β-(N,N-acetyl-ethylaminoco-ethylinthiazole are dissolved in 75 parts by volume of a mixture of 17 parts of glacial acetic acid and 3 parts of propionic acid. After adding 20 parts of 85% sulfuric acid,
Nitrosyl sulfuric acid (N, Os 11.5
%) was gradually added thereto and stirred at the same temperature for 4 hours.

The obtained diazonium salt solution was mixed with 4-phenyl-2-(
A mixture of 12.8 parts of N-diallylamino)-ki-thiazole, 20 parts of glacial acetic acid, 250 parts of water, 250 parts of ice and 1 part of amidosulfonic acid is slowly introduced. After the coupling is complete, the dye is filtered off with suction, washed to neutrality, and so
Vacuum dry at 'c. 18.0 parts of a dye of the following formula are obtained, which dyes polyester in deep violet shades with a high degree of light and heat set fastness.

In the same way, the dyes indicated by the diazo component and campling component in the table below are obtained.

Example 64 5-Amino-4-cyano-3-(2'-N-ethyl-N
-Fropionyl-amino)-ethyl-isothiazole (5.0 parts), acetic acid (22.5 parts by volume) and propionic acid Z5
Add to the mixture by volume and mix. After adding 10 parts by volume of 85% sulfuric acid, 6.4 parts of nitrosyl sulfuric acid (N20311.5%) was gradually introduced while stirring at 0 to 5°C, and the mixture was stirred at the same temperature for 4 hours. The obtained diazonium salt solution was mixed with 50 parts of water, 200 parts of ice, 10 parts by volume of 62% hydrochloric acid,
A solution of 3.9 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 20 parts by volume of dimethylformamide and 0.5 parts of amidosulfonic acid is introduced slowly.

After the coupling is completed, the dye is suctioned off, washed to neutrality, and then dried. 92 parts of a dyestuff of the following formula are obtained, which dyes polyester fibers in a clear bluish-red shade with good fastness properties.

Similarly, the compounds shown in the table below are obtained.

Example 106 5-amino-4-cyano-6-(2-(N-acetyl-
6 parts of N-ethylamino)-ethyl]-inthiazole were added to 35 parts of glacial acetic acid/propionic acid (3:1);
After adding 15 parts of 5% sulfuric acid, 8 parts of nitrosyl sulfuric acid (N20311.5%) is added dropwise at 0-5°C, and the mixture is stirred at 0-5°C for 4 hours.

6.6 parts of N-ethyl-N-(2-propy=;ruaminocarbonyloxy)-ethyl-m-toluidine was added to 60%
10 parts by volume of hydrochloric acid, 0 ethoxylic compounds of fatty alcohols
．． 6 parts and 120 parts of water. After adding 160 parts of ice, the diazonium salt solution described above is introduced.

After the end of the coupling, the resulting dye suspension is filtered,
The lachrymal residue is neutralized with water and dried under vacuum at 50°C.

Eight parts of a dyestuff of the following formula are obtained, which dyes polyester in a clear purple shade.

Continuation of page 1 @ Inventor Ernst Siefts Deutsche Federal Republic of Linaso 6700 Ludwigshalfen φzbu Straseff procedural amendment (voluntary) June 6, 1985 Patent Office Commissioner Shiga Gakudono 1° Case 0 Table 1 Japanese Patent Application No. 60-47616 2 Invention 0 Name Inchiazole azo dye 3 Person making amendment Related to the case Patent applicant Address Name (908) /<Suf Akchengesellschaft (Name) 4. Agent 5. Date correction of amendment order (Japanese Patent Application No. 47616/1983) Specification No. 46
Add the following below the page table.

"The λmaX (nm) value of the product of each example in dimethylformamide solution is as follows.

Example 1 562 Example 14 576/l 2 5
60 // 15 5791/ 3 557 // 1
6 580 // 4 555 // 17 5601/
5 568 1/ 18 561# 6 564 /
/ 19 560 // 7 569 /l 20 560 // 8 57
2 〃 21 565 // 9 565 1/ 22 56411 10 5
74 /l 25 5601/ 11 586 /l
24 571,, 12 578 〃25 572 1/ 13 589 // 26 571 Example 27
578 Example 47 562// 28 579 〃4
8 556 //29578 “ 49 559 //30578 “ 50 549 , /31578 ・51 545 // 62 578 // 52 551u33 57
8 ” 53 536 / l 34 545 // 54 544 // 35
534 // 55 534 // 36 535 //
56 539/' 37 537 // 57 54
2// 38 541 // 58 5621/ 39
542 // 59 5561/ 40 541 /
/ 60 5591/ 41 543 // 61 5
47 // 42 546 // 62 551u 46
547 〃63 5+6 // 44 553 // 64 544// 45
540 // 65 537/' 46 544 //
66 568 Example 67 568 Example 87 53
8// 68 541 // 88 537// 69
543 // 89 541 // 70 541 /
/ 90 5421/ 71 542 1/ 91 5
411/ 72 546 // 92 543// 7
3 547 // 93 546 // 74 556
〃 94547 U 75 534 # 95 553 // 76 538 // 96 534// 77
542 // 97 535 // 78 541 //
98 535// 79 541 /l 99 53
4tt Bo 536 tt 100 564/l 8
1 533 // 101 534# 82 544
# 102 554 // 83 542 // 103
554// 84 545 // 104 541/
/ 85 553 // 105 543 // B6
534 // 106 543 Example 107 55B
Example 116 555 // 108 547 // 1
17 538 // 109 545 // 118 5
43u 110 552 u 119 548// 1
11 546 1/ 120 539/I 112 5
46 // 121 601 // 113 543 /
/ 122 54ON 114 556 // 123
555N 115 541 # 124 548” Applicant Basf Akchengesellschaft Agent Patent Attorney Masao Kobayashi

Claims (1)

[Claims] 1. General formula (wherein R is a hydrogen atom, an 01-C4 alkyl group or an optionally substituted phenyl group, R1 is an allyl group, an optionally substituted alkyl group, a cycloalkyl group) group or aryl group R2 is an acyl group, R1 and R2 may also be combined with the nitrogen atom to form a saturated 5-negative or 6-membered ring or a diacylimide group, K means a residue of a coupling component ). 2, KH is the following formula (in the formula, R3 is a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, R4 is a hydrogen atom or the same as R5, R
5 is an optionally substituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl group, R
6 and R7 are a hydrogen atom, an alkyl group, an alkoxy group, a phenoxy group, an atom atom, an alkylsulfonylamine group, a dialkylaminosulfonylamino group, or an acylamino group, and R8 is a cyan group, a carbamoyl group, a nitro group, or a carbalkoxy group. , and R9 is an optionally substituted phenyl group, alkyl group, or aralkyl group) Claim 1
Compounds described in Section.